Dyestuffs for dyeing and printing fibre mixtures which contain fibres containing acrylonitrile



United States Patent DYESTUFFS FOR DYEING AND PRINTING FIBRE MIXTURES WHICH CONTAIN FIBRESCONTAIN- ING ACRYLONITRILE Roland Mueller antl-Julius Eisele, Ludwigshafen (Rhine), Germany, assignors to Badische Anilin- & Soda-Fabrlk Aktiengesellschaft, Ludwigshafen (Rhine), Germany No; Drawing. Application April 18, 1957 Serial No; 653,542

Claims priority,- application GermanyApril '18, 1956 6 Claims. (Cl. 821) 1 This invention relates to new' salt-like dyestuffs and especially to those salt-like dyestuffswhich areformed by precipitation of dissolved cationic (basic) dyestuffs with dissolved anionic (acid) dyestuffs (or conversely by precipitation of dissolved anionic dyestuffs with dissolved cationic dyestuffs) 'andwhich are suitable for dyeingand printing fibre mixtures which contain fibresof polyacrylonitrile or of co-polymers of acrylonitrile and fibres capablQ'Of being dyed with anionic dyestuffs.

Oneof'the most important problems which hasarisen from the increasing importance of modern synthetic fibres is that of dyeing or printing mixtures of thesefibres with the natural or'regenerated fibre varieties hitherto conventional and also mixtures of various newsynthetic fibres with each other. By reason of the differences, which are often very considerable, in the textile and especially the tinctorial properties of modern fibres, it is 2,922,690 Patented Jan. 26, 1960 with which the dyeing process itself can be commenced.

' immediately afterwards. For example, in contrast to the;

usually not possible to dye the various components of such fibre mixtures with the same dyestuffs. Hitherto it has often been necessary first to dye one kind of fibre in one dyebath, then to dye the second kind of fibre in a second dyebath, and thus to work consecutively in a plurality of baths. In this way there is not only an increased expenditure for apparatus but there are usually other dif ficulties, as for example the possibility of the formationof spots and of the partial and therefore speckled absorption of the dyestuff by the other kinds of fibres which are not to be dyed. Further Working operations are therefore unavoidable, serving for example for the stripping of the partially absorbed dyestuff, and by which in some cases the textile properties of the fibres may. be unfavorably influenced.

These difficulties exist inter alia also for the range of those fibre mixtures which are composed on the one hand of fibres containing acrylonitrile and on the other hand of natural, regenerated and/or synthetic fibres capable of being dyed with anionic dyestuifs, as, for example,

wool, silk, cotton, regenerated cellulose and/or synthetic I polyamides. Whereas the polyacrylonitrile and other acrylonitrile-containing fibres may be dyed above all with basic dyestuffs, there are in general used in the case for example of wool, acid dyestuffs; the two kinds of dyestuffs cannot, however, be used side by side in one dyebath because they produce precipitates which impair the dyeing process. In order to remedy this defect-without thereby having to resort to the two-bath method-it has been proposed to add to the dyebath, before the addition of the dyestuffs, adducts ofethylene oxide as dispersing agents; themutual precipitation of the acid and basic dyestuffs added consecutively (and separately) is thereby to be avoided. In this method, therefore, the dyer has to disperse consecutively the dispersing agent, the acid dyestuff and the basic dyestuif, each in a definite dosage, in

the dyebath before he can begin dyeing.

dyebath, i.e. are already preparedin'admixturje with the necessary additives-as for example dispersing agents; and

earlier methods in which azo and azomethine dyestuffs; were chromed on the fibre after dyeing, methods have become prevalent in which a ready-prepared chromiumcontaining dyestuff can be directly used by the dyers in: a quite uncomplicated way. Such dyestuffs capableof being used in a simple way have hitherto not been known for dyeing fibre mixtures which contained fibres of polymers. containing acrylonitrile.

The present invention, however, relates to dyestuffs of. salt-like nature which are suitable, by direct applicationin one dyebath, for the simultaneousdyeing of fibres of polyacrylonitrile and/ or other polymers containing'acry lonitrile on the one hand and'of natural, regenerated and/or synthetic fibres capable of being dyed with anionic dyestuffs on the other hand, i.e. of mixtures of fibres of the said kinds, from a single dyebath. These salt-like dyestuffs can also be used for the simultaneous printing of the said kinds of fibres by means of a single printing paste into which the dyestuifs have been incorporated. Dyestuffs of the said kind can be prepared, for example, by adding to a solution of a cationic dyestuff, advantageously at ordinary temperatures, the equivalent amount of a solution of an anionic dyestuff (the same, effect may naturally also be achieved conversely by pre-, cipitation of a solution of an anionic dyestuif with a cationic dyestutf) and filtering, drying and pulverizingthe precipitate formed. The pulverulent cationic and anionic dyestuffs may, however, also be mixed with eachother, made into a paste with water, dried and powered; in this case the precipitation process takes place during. the formation of the paste. In both cases it can be ad vantageous to incorporate with the salt-like dyestutf formed, from the start, an amount ofa dispersing agent which is equal to or greater than the amount of salt-like dyestulf. Examples of dispersing agents are sulfonated high-molecular organic compounds, ethoxylation products of organic substances, dextrines, or organic disulfone imides. Naturally, it is possible to use, instead of one cationic and one anionic dyestuif, two or more of each kind simultaneously. Afurther important variant of the invention consists in preparing salt-like dyestuffs from cationic and anionic initial dyestuffs of different shades by means of which there may be produced on mixtures.

of fibres containing acrylonitrile and fibres capable of being dyed with anionic dyestuffs, mixture or shot effects. It may furthermore also be advantageous to replace part ofthe cationic and/or anionic dyestuff or'dyestuffs by colorless cationic and/ or anionic substances, for example, dispersing agents, or to coernploysuch substances. This is recommended, vfor example, when, in the use of a dye: stufl salt obtained by the reaction of equivalent amounts of cationic and anionic dyestuffs, the shade ofcolor for example of the cationic dyestuff component is more pro: nounced than is desired in .the final dyeing by reason of its preponderant color strength. Moreover,the anionic dyestuff component (orcomponents) may, also be entirely omitted and. the cationic dyestuff component (or components) reacted instead only with colorless compound a (or compounds).

It is not necessary toreactrthe cationic and anionic colored and colorless components with each other in equimolecular amounts, but molar excesses of cationic or anionic substances may be present in the reaction, the salt-like dyestufr' then of'course containing this excess as an admixture.

For the production of the new dyestuffs theremay be used' as cationic or anionic initial dyestuffs all known dyestuffs of cationic or anionic character. For example basic (cationic) azomethine, polymethine or cyanine dyestuffs, including diazacyanine and hemicyanine dyestuffs furthermore diand tri-arylmethane, including indolyl diarylmethane dyestufis and anthraquinone dyestuffs of cationic character may be used as cationic components.

Di-, and tri-arylmethane dyestuffs, anthraquinone dye-- e su 7 in which K represents the cation of a cationic dyestufi ponent. The cationic and the anionic dyestuff components may each consist of a single cationic or anionic dyestuif, but may also include a plurality of cationic or anionic dyestuifs. With the new salt-likedyestufis there may be dyed or printed with advantage fibre mixtures, as for example flocks, threads, wovenor knitted fabrics which contain as components on the one hand fibres of polyacrylonitrile or of copolymers of acrylonitrile for example with vinyl chloride, vinylidene chloride, vinyl alcohols, vinyl acetate, acrylic esters, methaerylic esters and/or acylamide or methacrylamide, and on the other hand natural, regenerated or synthetic fibres capable of being dyed with anionic dyestuffs, as for example wool, cotton, fibres of regenerated cellulose and/or of synthetic polyarnides. Fibre mixtures which are composed of a plurality of kinds of fibres containing acrylonitrile and a plurality of fibres capable of being dyed with anionic dyestuffs are also suitable for dyeing or printing with the new dyestuffs. In the mixtures, the said fibres can be used in all proportions, i.e. not only in' a proportion of 50:50, but also in other proportions as 45:55, 40:60, 30:70, 20:80 or 10:90 and vice versa. 1

The new dyestuifs, if desired containing the said cationic or anionic admixtures, are simply added to the dyebaths with which fibre mixtures of the above-mew tioned kind can then be directly dyed by known methods. The dyeing can be carried out at temperatures of 95 to 130 C., preferably at 97 to 110 C.; at temperatures lying above 100 C., dyeing is under a pressure of up to 2.5 atmospheres overpressure. Printing with the new dyestuifs may also be carried out by known methods. During the course of the dyeing or printing process, the cations formed by dissociation from the dyestufi salts go on to the fibres containing acrylonitrile polymers and the anions also formed go on to the fibres capable of being dyed with them. Obviously there may also be coemployed inorganic salts, and auxiliaries, as for example fatty alcohol sulfonates, in the dyebaths and printing pastes. Following the dyeing or printing there may advantageously be carried out a treatment of about a quarter of an hour with anionic auxiliaries, as for example sulfonation products of high molecular organic compounds, in a temperature range of about 40 to 60 C. (but not above 90).

With the aid of the new dyestuffs it is possible to obtain unitary, fullshade dyeings and prints of all tones and excellent fastness properties, on fibre mixtures of individual fibres of any kind in a simple way.

The following examples will further illustrate this inyention but the invention is not restricted to these examples. The parts specified are parts by weight.

Example I 5 parts of the cationic dyestutf of the formula:

and 5 parts of the anionic dyestufi of the formula:

both in the powdered state, are mixed with 10 parts of component and A th nion of an a i i dyestufi the condensation product derived from 2 mols of the sodium salt of naphthalene-Z-sulfonic acid and 1 mol of formaldehyde, the resultant mixture made into a paste with 20 to 40 parts of water, dried and ground in a ball mill. A blue dispersion dyestufi is obtained which-can readily be dispersed in water and gives dyeings of excellent fastness properties on fibre mixtures of fibres containing acrylonitrile and fibres capable of being dyed with anionic dyestuffs.

In the same way dispersion dyestuffs can be prepared from the dyestuffs described in the co-pending U.S. patcut applications Ser. No. 587,503, filed May 28, 1956, by Helmut Pfitzner, Hans Baumann, Julius Eisele and Wilhelm Federkiel, and Ser. No. 617,706, filed October 23, 1956, by Wilhelm Brunkhorst, Emil Kern and Hans Baumann as cationic initial dyestufis and the 1:1-complex chromium compound of the monoazo dyestufi of the formula or a dyestufi described in the U.S. patent specifications Nos. 2,708,193 and 2,685,595 and in the copending U.S. patent applications Ser. No. 403,446, filed January 11, 1954, by Helmut Pfitzner and Otto Kaufmann and Ser. No. 472,244, filed November 30, 1954, by Helmut Pfitznet and Otto Kaufmann, as anionic initial dyestuffs.

Example 2 A dispersion dyestufi is prepared as described in Example 1 from a cationic dyestufi of the formula and the water-soluble lzl-complexchromium compound of the monoazo dyestutf of the formula the anionic dyestuff described in Example 1 maybe used instcad of the said acid dyestutf as the dyestuti.

' Example For the production of a dispersion dyestuff there are used as initial dyestufi's a cationic dyestufi of the formula and an anionic lzl-complex chromium compound of the monoazo dyestufi of the formula HOOC OH April. If], 195-7, by Ha'ns'Bau'mann, Friedrich Arnemann,

Iulius Eisele and Wilhelm Federkiel for The Dyeing of Polyacrylonitrile and CQpQlymers of Acrylonitrile as initial dyestufi. Similarly the'dispersion dyestuff can be preparedfrom thecationic dyestufis described in this example and the anionic dyestuffs of US. patent specifi cation" No; 1,801,745. t V 4-: 1 Example4 The; procedure of paragraph 1 of Example 3 is followed, but instead of the cationic dyestuff therein specified there is used a dyestuff of the formula H, CH,

A yellow dispersion dyestufi is obtained which gives dyeings of excellent fastnes's properties on the said fibre mixtures; I

- Example 5 A solution of 5 parts of the cationic dyestufl? specified in Example 4 in 250 parts of water is precipitated with a IT solution of 5 parts of the lzl-complex chromium compound formed by c'hroming from the monoazo dyestufi of the formula HOaS I SOaH sulfo nic acid phenylamide, in 280 parts of water at room or somewhat elevated temperature, the precipitate formed is separated, dried and powdered. A yellow dispersion dyestufi is obtained.

r medwi'th" 1 mol of- 1-carboxy-2-hydroxybenzene-S- H H'ehnut Pfitzner and'Otto Kaufmann.

Further" dispersion dyestuffsKean be prepared in the same way' from I the cationic dyestuffs specified iii-Ex amples 1 to 3 and the anionic dyestuff described in the second paragraph of Example 2.

Example 6 A dispersion dyestuff is prepared as described in Example 1 from the cationic dyestuif of paragraph 1 of Example 3 and an anionic dyestufi of the formula O lOr-NH-CO-O 01 It gives yellow dyeings of very good fastness'iproperties on the fibre mixtures previously described.

'In1the same way dispersion dyestuffs may be prepared from: the cationic dyestufis specified intExamples 1 to 5 and the anionic dyestuffs specified in French patent spec ification No. 1,026,865.

Example 7 A By the method of Example 1 there is obtained from the cationic dyestuff specified in paragraph 1 of Example I 2' and the anioniedyestuff of the formula soar a red dispersion dyestuif which gives on the said fibre mixtures dyeings :of very good fastness properties. In the-same way a red dispersion dyestuff is obtained by using as anionic dyestufi the 1:2-chrornium complex of n the monoazodyestuif of the formula Further dispersion dyestuffs can be prepared froni'the cationic dyestuffs specified in paragraph 1 of Example 2 and the anionic-'dyes'tuifs described in French patent specification No. 894,039 and the copending U.S patent application Serial No. 515,554, filed June 14, 1955,, by

Example 8 A dispersion dyestuff is prepared as described in Example 1 from the'cationic dyestufi specified therein (in paragraph 1') and the direct dyeing anionic dyestuif of the formula i A blue dyestufi is obtained which may be readily disperse'd in water.

Instead of the said cationic dyestufi there may similarly be used also the cationic dyestufi of Example 2 parts of dextn'ne.

'7 and Example 3, paragraph 1, and-instead ofthe said anionic dyestufi, the dyestuffs of the formulae 1 a and son; 7

as initial dyestufis.

Example 9 A red dispersion dyestuft is prepared by the method of Example 1 from a cationic dyestuff of the formula and the anionic dyestufi specified in Example 2.

Example 10 A salt-like dispersion dyestufi is prepared according to the process of Example 1 from Spirit Blue (Schultz- Lehmann, Farbstofitabellen, 1931, volume 1, No. 792: Colour Index, 1924, No. 689) as cationic initial dye stud and one of the anionic dyestufis specified in Example 1 or the dyestutf Orange '11 (Schultz-Lehmann,

initial dyestuti.

In the same way, dispersion dyestulfs can be prepared from the cationic dyestufisspecified in Example 1 and Orange II. Example 11 Dispersion dyestuffs can be prepared from the cationic dyestuffs specified in Example 1- by the use of copper,

nickel or cobalt phthalocyaninc tetra-sulfonic acids or their carboxylic acids as anionic initial dyestuffs, as described.

Example 12 The dispersion dyestufis specified in Examples 1 to 4 and 6 to 11 may also be prepared by the method of claim Example 13 Instead of the dispersing agent specified in Example 1, there may also be used for the preparation of the dispersion dyestufis in Examples 1 to 4 and 6 to 11 10 parts of the condensation product of cresol formaldehyde resin with the sodium salt of Z-hydroxynaphthalene- 6-sulfonic acid, sodium sulfite and formaldehyde or 10 I Example 14 Into a dyebath of 1 part of the dyestufi salt prepared according to Example 1, 1 part of thecondensa'tion product of 10 parts of naphthalene-Z-sulfonic acid with 1 part of formaldehyde and 4 parts of 85% formic acid- ,in 5,000 parts of water, 100 parts of a fabric of 50 parts of polyacrylonitrile fibres and 50 parts 'ofwool is introduced at about 50? C. The bath is heated to 100 c- N=N -NH-oo-oH,-co-cm mo V i like dispersion dyestufis specified in Examples 1 to 13 can loc.cit., No. 189: Colour Index No. 151) as anionic Example 14 are dyed'for'lhours at in aibath- 1 but without the addition of the dispersing agent therein ,described.

C. and dyeing cOntinued fSi- SQ minutes at this temperature; the fabric is then rinsed and dried the usual way. Powerful dyeings of excellent "fastness proper- 29 ties are thus obtained on both kinds of fibres.

90 to 10 parts of wool or of 10 to 90 parts of polyacrylonitrile fibres and 90 to 10 parts of fibres of polyhexamethylene diamine adipate or of polycaprolactam in general can be dyed in the same way. The saltbe used. Example 1 100 parts ofone of the fibre mixtures specified in' of 1 part of a dispersion dyestufi prepared according to Example 2, 1 part of the sodium salt of oleyl polyglycol ether sulfate, 20 parts of sodium sulfate and 2 parts of sulfuric acid in 4,000 parts of water. Mixed fabrics of 45 parts of wool and parts of a copolymer' of 93' parts of acrylonitrile and 7 parts of methylmethacrylate' can be dyedsimilarly. v

0 Example 16 100 parts of mixed woven or knittedfabric of parts of a copolymer of 93 parts of acrylonitrile and 7 parts of methyl niethacrylate on the one hand and 40 parts of -wool 011,40 parts of fibres .of. polycaprolactam or iofi' polyhexamethylenejdiagnine adipate on the' l other hand'are dyedsfor 20 minutes at 109 C; in a high temperature dyeing apparatus in a bath of 0.2 part'of the salt-like dispersion dyestufi prepared according to paragraph 1 of Example 3, 1 part of the sodium salt of oleyl polyglycol ether sulfate, 20 parts of sodium sulfate and 2 parts of sulfuric acid in 4,000 parts of water. Fibre mixtures of all of the kinds described in Examples 1 to 7 and 9 to 13 can be dyed in-the same way.

7 Example 17 1 from the cationic dyestufi named in Example 3, section 1 and the anionic dyestuff of the formula mot c N=N 1.4 parts of the anionic dyestuff of the aforesaid formula and 20 parts of sodium sulfate in 4,000 parts of water. The salt-like dyestufi described in Example 4 can also be used.

Example 18 parts of the salt-like dyestuff named in Example 3, section 1, but prepared by the method described in Example 12 in the absence of a dispersing agent, parts of thiodiglycol, 20 parts of tartaric acid, 650 parts of crystal gum and 300 parts of water of 80 C. are made into a paste in known manner and this paste is used for printing a mixed fabric of 50 parts of wool and 50 parts of fibres made of a copolymer from 93 parts of acrylonitrile and 7 parts of methyl methacrylate. For finishing the prints are dried and steamed for 30 minutes at 101 to 102 C.

We claim: 1. A salt-like dyestulf of the general formula in which K represents the cation of a member of the group of tn'phenylmethane dyestuffs free from sulfonic acid groups and of cationic character, cyanine and diazacyanine dyestuffs and A represents the anion of a member of the group consisting of indolyl diphenylmethane, azo dyestufis and their complex compounds with a metal of an atomic number between 24 and 29 which azo dyestufis and complex compounds contain at least one watersolubilizing group selected from the class consisting of sulfonic acid, carboxylic acid, sulfonic acid amido and carboxyhydroxybenzene sulfonic acid amido substituent dyestuffs having anionic character.

2. The salt-like dyestufi obtained by the reaction of the cationic dyestufi of the formula and the anionic dyestutf of the formula oa s 3. The salt-like dyestuff obtained by the reaction of the cationic dyestufi of the formula and the anionic 1:1 complex chromium compound of the monoazo dyestutf of the formula 4. The salt-like dyestufi obtained by the reaction of the cationic dyestutf of the formula and the anionic 1:1-complex chromium compound of the monoazo dyestutf of the formula HO 0 c on E30 OlNHOP 2\ NH trol s N=N/ g 5. The salt-like dyestuff obtained by the reaction of the cationic dyestuif of the formula and the anionic lzl-complex chromium compound of the monoazo dyestuff of the formula H O HOOO References Cited in the file of this patent UNITED STATES PATENTS 2,760,841 Salvin et al. Aug. 28, 1956 2,767,166 Strabel et al. Oct. 16, 1956 FOREIGN PATENTS 136,921 Switzerland Feb. 17, 1930 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,922,690 January 26, 1960 Roland Mueller et al.

tified that error appears in the-printed specification It is hereby oer ng correction and that the said Letters of the above numbered patent requiri Patent should read as corrected below.

Column 5, line 44, for that portion of the formula reading "N-CH CH-N" read C-CH CHN column 10, line 35, claim 5, for that portion of the formula reading "NCH=CH-N read C-CH=CHN Signed and sealed this llth day of October 1960.

(SEAL) Attest:

KARL H. AXLINE Attesting Officer ROBERT C. WATSON Commissioner of Patents 

6. A METHOD OF DYEING POLYMERIC ACRYLONITRILE-CONTAINING FIBRES AND WOOL FIBRES IN MIXED TEXTILES WHICH COMPRISES PRECIPITATING FROM AN AQUEOUS SUSPENSION A SALT OF A CATIONIC DYESTUFF AND AN ANIONIC DYESTUFF IN THE PRESENCE OF A DISPERSING AGENT, INCORPORATING SAID WATER-WETTED PRECIPITATED SALT IN A FINELY DIVIDED SUSPENSION IN AN AQUEOUS DYEBATH AND SUBJECTING THE MIXED FIBRE TEXTILE TO CONTACT WITH SAID SALT SUSPENSION AT A TEMPERATURE OF FROM 95-130*C. FOR A TIME SUFFICIENT TO COLOR THE FIBRES IN SAID TEXTILES. 